Determination of zirconium and hafnium with xylenol orange and methylthymol blue

Both Xylenol Orange and Methylthymol Blue are highly selective and sensitive reagents for zirconium and hafnium forming intensely red complexes in an acidic medium. The factors affecting the color formation have been studied. The properties of the complexes have been determined and compared. In general, zirconium forms a more stable complex with the two dyes than hafnium, and Xylenol Orange forms a stronger complex with either zirconium or hafnium than Methylthymol Blue. Hydrogen peroxide can completely mask the zirconium complexes of either dye but only slightly affects the hafnium complex of Xylenol Orange. Zirconium and hafnium can both be determined without separation using peroxide as a masking agent and sulfate as a demasking agent. A bleaching reaction was observed when small amounts of hafnium were added to the red zirconium complex of Methylthymol Blue in 2.4 N perchloric acid or a small amount of zirconium was added to the red hafnium complex of Methylthymol Blue solution at pH 2 to 3.     

双波长分光光度法测定溴化十六烷基三甲基铵

以二甲酚橙为显色剂,采用双波长分光光度法测定水中溴化十六烷基三甲基铵。实验确定的测定条件为:最大吸收波长为590 nm,等吸光度点的波长点为509 nm,选择pH为6.86的Na3PO4-Na2HPO4缓冲溶液3.50 mL,0.80 g/L二甲酚橙显色剂2.0 mL,显色时间为5 min。试剂加入顺序对测定结果基本无影响。CTMAB的质量浓度在0~1.2 mg/mL范围内符合比尔定律,标准曲线为ΔA=0.0123ρ 0.0825,相关系数为R2=0.9998,样品加标回收率为99.6%~101.3%。     

Chelate formation of zirconium with xylenol orange and semi-xylenol orange

The composition, formation constants, and molar absorptivities of the chelates of zirconium ion wtih xylenol orange and semi-xylenol orange are investigated spectrophotometrically in strong acid medium at ionic strength 3.0 (NaClO₄ and HClO₄). The data obtained were processed with a newly-constructed computer program and with LETAGROP/SPEFO. In the zirconium—xylenol orange system, Zr · H₃ L, Zr· H₄L, and Zr₂ · L are present with logarithmic overall formation constants of 37.80, 38.68, 43.47, and molar absorptivities of 3.10 × 10⁴ (485 nm), 5.98 × 10⁴ (528 nm), 9.50 × 10⁴ (551 nm) I mol^-1 cm^-1, respectively. The chelates Zr · L and Zr · HL were found in the zirconium—semi-xylenol orange system with logarithmic overall formation constants of 26.25 and 27.56, and molar absorptivities of 5.70 × 10⁴ (532 nm) and 8.30 × 10⁴ (535 nm) 1 mol^-1 cm^-1, respectively. Semi-xylenol orange is more sensitive and reliable than xylenol orange as a spectrophotometric reagent for zirconium.     

Absorption characteristics of xylenol orange

Absorption characteristics of Xylenol Orange have been reinvestigated for the purpose of its spectrophotometric estimation. The molar absorption coefficient of Xylenol Orange at 580 nm and pH 10.0 is 3.12 x 10(4) l.mole(-1), cm(-1).     

Polarographic study of xylenol orange

In neutral medium the ring carbonyl group of xylenol orange is reduced in two one-electronsteps at a dropping mercury electrode. Step I is nearly reversible, but step II strongly irreversible. The half-wave potentials of both steps depend on pH, for the products of reduction, the dye radical formed in step I and the OH group produced in step II, behave as acids. From the E_1/2 vs. pH dependence, the pK of the dye radical is found to be 9.5, that of the hydroxy compound 5.6. On progressive acidification the height of step II continuously decreases, while that of step I increases. In solutions with pH<2, only a single (according to logarithmic analysis) one-electron, but overall (according to coulometry) two-electron step results. The ratio i^I/i^II for the two steps increases when larger amounts of alkali metal ions are added. The exaltation of the first wave at the expense of wave II is explained by an acid-dependent dismutation of the dye radical formed during the first one-electron step.     

Complex formation of zirconium and hafnium with xylenol orange

The factors affecting the formation of zirconium and hafnium complexes of xylenol orange (XO) in perchloric acid have been examined. The optimum acid concentration for both systems is in the range 0.2–0.5 M HClO₄. When excess of metal is present, an initial complex with (XO) : metal ratio of 1 :1 is formed; this complex then undergoes an acid-dependent reaction, taking approximately 2 h to reach completion. Rate constants for this reaction have been determined. When excess of xylenol orange is present (i.e.(XO) : metal ? 2) a 2 :1 complex is formed which does not undergo further reaction. Extinction coefficients are given for the various complexes.     

Spectrophotometric determination of zirconium in steels with xylenol orange

Zirconium (0.005–0.25%) is determined after acid dissolution of the steel, and fusion of insoluble matter with sodium carbonate and sodium hydrogensulphate. Niobium and other interfering ions are removed by mercury cathode electrolysis. Residual small amounts of iron(III) are masked with ascorbic acid.     

Separation and acid equilibria of xylenol orange and semi-xylenol orange

A mixture of Xylenol Orange (XO) and Semi-Xylenol Orange (SXO) was chromatographed on a cellulose column and ion-exchanged with Diaion SK-1 resin. XO and SXO in the acidic forms were titrated with sodium hydroxide to determine the basicities and the acid formation constants. The absorption spectra of XO and SXO were measured over a wide pH range, and were used for the calculation of acid formation constants, molar absorptivities, and the effect of ionic strength on the activity of XO. The purity of a commercial XO was measured by absorption spectroscopy, and it was found that the sample contained 36.3% of XO and 17.2% of SXO. Pure XO and SXO form a 1:2 and a 1:1 complex respectively with Zn(II). On the basis of these data the ionic structure of XO and SXO have been compared with those of Cresol Red and iminodiacetic acid, and discussed.     

Determination of trace amounts of zirconium in silicates by cation-exchange chromatography and spectrophotometry with xylenol orange

An ion-exchange scheme and colorimetric determination with Xylenol Orange are used for estimating traces of zirconium in silicate rocks.     

Spectrophotometric determination of chromium with xylenol orange and methylthymol blue

A new simple and sensitive method for determining traces of chromium is described. Xylenol Orange and chromium(III) form a red complex at pH 3 on heating in boiling water for 20 min. The molar absorptivity is 19.0 x 10(3). No catalytic action of the bicarbonate ion, carbon dioxide, or chromium(II) generated by metallic zinc was observed. Methylthymol Blue is a less sensitive reagent for chromium, the molar absorptivity being 11.5 x 10(3).     

Determination of trace amounts of thallium by adsorptive cathodic stripping voltammetry with xylenol orange.

Trace amounts of thallium(I) can be determined using adsorptive cathodic stripping voltammetry in the presence of Xylenol Orange (XO). The reduction current of the thallium(I)-XO complex ion was measured by square-wave cathodic stripping voltammetry. The peak potential was at -0.44 V vs. Ag/AgCl. The effect of various parameters (pH, ligand concentration, accumulation potential and collection time) on the response are discussed. The response was linearly related to the thallium concentration in the range 0.5-110 ng ml(-1) and 110-2000 ng ml(-1). The limit of detection was 0.2 ng ml(-1). The relative standard deviation for the determination of 80 ng ml(-1) thallium was 2.8%. Many common anions and cations did not interfere with the determination of thallium. The interference of lead was reduced by the addition of 0.003 M sodium carbonate. The voltammetric procedure was then successfully applied to the determination of thallium in various complex samples.     

Simultaneous spectrophotometric determination of o-cresol red, semi-xylenol orange and xylenol orange

A direct simultaneous spectrophotometric method for the determination of o-Cresol Red (CR), Semi-Xylenol Orange (SXO) and Xylenol Orange (XO) in mixtures in the presence of other components usually found in commercial SXO and XO reagents is presented. The method of selecting the most advantageous conditions for the spectrophotometric determination of the three dyes in different mixtures is given.     

Formation constants of alkaline-earth metal complexes with xylenol orange and methylthymol blue

The complexes of the alkaline-earth metals with Xylenol Orange and Methythymol Blue have been studied. Three 1:1 and two 2:1 (metal:ligand) complex species for each indicator and each element have been found to be formed in aqueous solutions, and the formation constants and the arrangements of these complexes have been determined.     

Equilibria of iron(III) complexes with xylenol orange and methylthymol blue

A potentiometric and spectrophotometric study of Fe(III) complexes with Xylenol Orange (XO) and Methylthymol Blue (MTB) has been made. The formation constants for the Fe(III) complexes with XO and MTB were determined. Evidence was found for the formations of 1:1 and 2:1 complexes (metal:ligand) and it was assumed that protonated and hydroxo-complexes exist in addition to the simple complex in each case. The hydroxo-complexes are stable over the pH range of 7–12. Suggestions are made concerning the probable structures of these complexes.     

Rapid photometric determination of neptunium with xylenol orange after extraction with Aliquat-336

A rapid method based on the extraction of neptunium(IV) by Aliquat-336 followed by its direct photometric determination in the organic phase employing xylenol orange is reported. Optinum conditions have been established for the extraction and determination of as little as 0.4 ppm of Np. The molar absorptivity of the red-coloured neptunium complex at 535 nm is 49535±361 1·mol⁻¹·cm⁻¹. Unlike the well-known absorptimetric method for estimating NP(IV) with Arsenazo III, this method tolerates many-fold excesses of fluoride, nitrite, nitrate, phosphote, oxalate as well as UO ₂ ²⁺ , Pu⁴⁺, Zr⁴⁺, etc., which are some of the major contaminants associated with neptunium during its reprocessing.     

Radiation chemistry of xylenol orange in aqueous solutions at different acidities

The radiolytic decolourization and peroxide formation have been studied in aqueous solutions of xylenol orange (XO) at different acidities. The G(-XO) increases from 0.78 at pH 11, to 3.70 at pH 3. The peroxide yield also increases from 1.19 at pH 11, to 3.34 in 0.025 mol dm^-3 H₂SO₄. In alkaline solutions only the OH^. decolourizes XO whereas in acidic solutions both the H and OH^. decolourize XO though G(-XO) due to H-atoms is less. The ionization of the phenolic group in XO influences the e^-_aq reaction with it. In alkaline solution, the oxidized and reduced XO formed by OH^. and e^-_aq reactions, respectively, react together regenerating original XO. Near 0.025 mol dm^-3 H₂SO₄, there is an abstraction of H-atom from XO by HO₂ whereas at other acidities, H₂O₂ is formed by disproportionation of peroxides. Reaction schemes have been given to explain the various radiolytic yields.     

Detection of rare earth elements by post-column reaction with xylenol orange and cetylpyridinium bromide

Rare earth elements have been separated by HPLC on octadecyl-bonded silica gel, dynamically modified with ammonium dodecylsulfate, using aqueous solutions of α-hydroxyisobutyric acid as mobile phase. The requirements and characteristics of post-column reaction with xylenol orange and cetylpyridinium bromide were investigated and optimized, and the reaction found to be highly sensitive and sufficiently rapid. The absorbance of the complex at 598 nm was not affected by the presence of α-hydroxyisobutyric acid at concentrations of the latter up to 150 mmol/l; at higher concentrations of the acid, the absorbance decreased slightly. For most of the rare earth elements the response was linear up to 0.2 mmol/l; the relative standard deviation of peak area was, typically, ～1 %. The sensitivity of the method was usually better than 1 μg/ml. The results obtained from the determination of lanthanum, cerium, praseodymium, and neodymium in samples of apatite and bastnesite were in a good agreement with those obtained by ICP-AES.